JP6173001B2 - Iron supply material and iron supply method - Google Patents

Description

  The present invention relates to an iron supply material capable of appropriately supplying iron to environmental water and an iron supply method using the iron supply material.

  There is a word "forest is a lover of the sea". This is a word that expresses the fact that the sea is activated by the iron flowing from the forest. However, the actual Japanese sea has the sixth largest sea area in the world, but it has been burned in anemia, making it difficult to produce kombu, and seafood. These factors vary, but the lack of iron flowing from the forest is one of them.

On the other hand, there are areas on the earth where plants do not grow in the sea. Although the sea area is rich in nitrogen and phosphorus, phytoplankton does not increase and chlorophyll concentration tends to be low. This is due to the lack of iron in micronutrients.
Therefore, supplying iron can increase the plant plank, grow shrimp, oysters and shellfish that feed on it, and also make it possible to breed kombu and seaweed.

  Here, if we consider that useful resources such as kombu and seaweed are cultivated and used as a food source by supplying iron continuously, a carbon source that feeds macroalgae is necessary to grow macroalgae. However, this uses carbon dioxide in seawater. As a result, the carbon dioxide concentration in seawater decreases. And carbon dioxide in the atmosphere dissolves in seawater to replenish it. When such a carbon dioxide consumption cycle is established, the dissolution rate of carbon dioxide dissolved in seawater increases, which can ultimately contribute to the prevention of global warming.

That is, increasing the iron content in seawater has the following effects.
(1) Increase chlorophyll.
(2) Seaweed and seaweed breed.
(3) Oxygen gas is released from seaweed.
(4) Purify water, decompose sludge, and improve the transparency of the sea.
(5) Prevent firewood burning.
(6) Fish and shellfish breed.
(7) There is absorption of carbon dioxide by seaweed.
(8) Promotion of dissolution of atmospheric carbon dioxide into seawater.
(9) Prevent global warming.
Etc.

In addition, supplying iron into the environmental water has the effect of purifying water quality, forming seaweed beds in seawater, and proliferating seafood and seaweeds. However, since iron in seawater exists only in a very small amount, a technology for continuously supplying high-concentration iron that can be absorbed by organisms in seawater is demanded from an earth engineering standpoint.
That is, the iron concentration in land water is on the order of several mg / L, whereas the iron concentration in sea water is on the order of several ng / L, which is only a part per million of land water.

  Iron is an essential element not only for humans but also for other organisms. In particular, in the oyster, kelp, seaweed, and seaweed aquaculture industries, the supply of iron is a serious problem, and although various methods have been studied so far, no definitive iron supply material has been developed.

  For example, in Patent Document 1, it is eluted from steelmaking slag by installing in a water a mixture containing steelmaking slag and slag containing fulvic acid, preferably a slag containing 0.002% by mass or more of fulvic acid content. A technique is disclosed in which iron (divalent iron) to be produced and fulvic acid contained in the clay are combined to produce iron fulvic acid, and this fulvic acid iron can be supplied into water for a long period of time.

  Further, Patent Document 2 forms a backfill portion having an average water depth in the range of 2 to 15 meters at low tide by sinking an iron-containing substance such as steelmaking slag as a submerged material on the sea floor. A technique for embedding an iron fulvic acid elution unit in the section is disclosed. In particular, this iron fulvic acid elution unit is a solid organic state obtained by collecting and solidifying sediments such as humic substances deposited on the bottom of a dam lake in an ion-eluting container made of palm fleece fibers, and containing iron such as steelmaking slag. Contains the substance. In addition, this iron-containing substance is alkali-adjusted by making it react with a weakly acidic solid organic state, and can delay elution.

  Furthermore, Patent Document 3 stabilizes iron fulvic acid by placing a coconut fiber bag filled with waste wood chips mixed with at least one of coal molten ash or converter slag in the sea. Technologies that can be supplied automatically are disclosed.

JP 2011-155993 A JP 2010-110255 A Japanese Patent No. 3829140 JP 2011-153353 A

  Here, in the techniques described in Patent Documents 1 to 3, it is important to use steelmaking slag and the like. However, the steelmaking slag may contain harmful metals and has recently been used. There are various kinds of self-suppressed metals, and there is a concern about bioconcentration in fish.

  With respect to this problem, Patent Document 4 contains iron powder, iron oxide, carbon and divalent iron ions and an organic acid that forms a chelate without using steelmaking slag, and supplies iron ions into water. An iron powder mixture is disclosed.

However, in the technique described in Patent Document 4, it is essential to use an organic acid that forms a chelate with a divalent iron ion, which is an expensive drug, and there is a problem of cost.
Furthermore, as a result of investigations by the inventors, even if iron powder, iron oxide and carbon are directly applied to a substance containing fulvic acid as described in Patent Documents 1 to 3, iron fulvic acid is effectively produced. I found out that there is no problem.

  Therefore, as a result of the intensive study of the new problem by the inventors, humus is selected as a substance containing fulvic acid, and furthermore, by using an iron material having a predetermined oxygen content or less and a carbon material in combination, It has been found to be economical and to effectively produce iron fulvic acid.

  The present invention has been developed in view of the above-described present situation, and provides an iron supply material that is high in safety and excellent in economic efficiency, and at the same time has a high generation rate of iron fulvic acid, together with an iron supply method using the same. For the purpose.

That is, the gist configuration of the present invention is as follows.
1. An iron supply material for supplying iron to environmental water, comprising humus, a carbon material, and an iron material having an oxygen content of 1% by mass or less, and at least a part of the carbon material and the iron material are in contact with each other Iron supply material.

2. The iron supply material according to 1, wherein the iron material is pure iron having an oxygen content of 1% by mass or less.

3. ^3. The iron supply material according to 1 or 2 above, wherein the electric conductivity of the carbon material is 10 ³ Ω · cm or less in volume resistivity.

4). The iron supply material according to any one of 1 to 3, wherein the carbon material is at least one selected from carbon fiber reinforced plastic, expanded graphite sheet, charcoal, graphite material, carbon material, bamboo charcoal, and carbon fiber.

5. The iron supply material according to any one of 1 to 4, wherein the iron material and the carbon material are used as a center of the iron content supply material, and the humus is disposed on the outer periphery thereof.

6). 6. The iron supply material according to any one of 1 to 5 above, wherein the iron content is wrapped with a self-shrinking binding material from the outside of the humus.

7). The iron supply material according to any one of 1 to 6 above is installed in at least one environmental water selected from among a river, a lake, and the sea, and iron is supplied to elute iron into the environmental water as an iron complex. Method.

  According to the present invention, it is possible to provide an iron supply material that is high in safety and excellent in economic efficiency and at the same time has a high generation rate of iron fulvic acid, together with an iron supply method using the same.

It is the figure which showed the example of the iron supply material which supplies iron with respect to the environmental water according to this invention. It is the figure which showed one example of the structure of the continuous iron supply material according to this invention. It is the figure which showed one example of the structure of the unit of the continuous iron supply material shown in FIG. It is the figure which showed one example of the structure of a carbon material and an iron material among the continuous iron supply materials according to this invention. It is the figure which showed the example of arrangement | positioning of the iron content supply material according to this invention. It is the figure which showed the humus used for the Example. It is the figure which showed the iron material used for the Example.

Hereinafter, the present invention will be specifically described.
As shown in FIG. 1, the present invention is an iron supply material that supplies iron to environmental water, including humus, a carbon material, and an iron material having an oxygen content of 1% by mass or less, At least a part of the carbon material and the iron material are in contact with each other.

  The iron material used in the present invention is not particularly limited as long as it has an oxygen content of 1% by mass or less and contains an iron component, that is, metallic iron, and is an alloy containing Fe such as an iron nickel alloy. However, it is most desirable to use pure iron in view of the substances released to the environment.

  Moreover, since the iron material used by this invention is calculated | required that a contact area with a carbon material is large, it is desirable to have a plate shape and a cylindrical shape with a plane or a curved surface. In particular, it is preferable to use a linear or rod-shaped iron material. A film-like iron plate can also be used if it is limited in time.

On the other hand, the carbon material used in the present invention is not particularly limited as long as it contains a carbon component, and may contain graphite structure carbon. Further, the electric conductivity of the carbon material is preferably 10 ³ Ω · cm or less in terms of volume resistivity. This is because the elution amount of iron ions is easy to control.

  The carbon material can be appropriately selected according to the elution amount of iron ions, the installation location, etc. without being limited in purity or shape. That is, the carbon material may be a woven fabric made of carbon fiber, but durability is important when used in a severe sea area such as a wave. Therefore, carbon fiber reinforced plastic (hereinafter also referred to as CFRP) is desirable. Furthermore, if it is a limited sea area where waves are not severe, a carbon material sheet made from an expanded graphite sheet, charcoal, graphite material, carbon material, bamboo charcoal and the like can also be used. In addition, conductive rubber containing carbon components, graphite-containing paints, and the like can also be used.

  Furthermore, although the shape of the carbon material is not particularly limited, since it is desired that the contact area with the iron material is large, it is preferable to use a carbon fiber woven fabric, a plate shape, or a film shape rather than a powder or grain shape. Is preferable.

  In the present invention, the humus is a soil animal of various sizes, such as microorganisms such as bacteria and earthworms, in which organic matter produced by above-ground plants in the forest ecosystem becomes deciduous trees, deciduous leaves, and twigs and accumulates on the surface. Although it is a soil that has been decomposed (deciduous leaf decomposition) due to biochemical metabolic action by, it is not strictly soil, but in general, what is called humus or humus is used.

  Naturally made humus is often biased towards nitrogen, but phosphoric acid and potassium may be supplemented by the action of earthworms, other animal feces and microorganisms. In addition, although the humus produced artificially has the component adjusted artificially, there is no problem in the use to this invention.

Here, leaves that tend to become humus are deciduous trees and broad-leaved trees, such as deciduous trees and broad-leaved trees, that are easy to ferment.
Naturally made humus takes more than a year or two to ferment, but when it is made artificially, it is easy to ferment using rice bran. Therefore, the period until completion is shortened to about two months. As a result of measuring the iron content in the purchased humus using an X-ray analyzer, the iron content in the humus was about 0.5% by mass.

As described above, the properties of humus vary depending on the raw materials and the production method, but it is important to select the most suitable humus.
Specifically, the mulch is preferably one that has thick leaf flesh such as cypress, sardine, arakashi, beech, kunugi, konara, chestnut, and deposits fallen leaves of broad-leaved trees and is appropriately fermented. The condition to be used should be fermented to the extent that it can be easily broken by hand, and the ones that use fallen leaves of the beech family such as Japanese oak and chestnut are especially best. Furthermore, what contains iron, potassium, calcium, magnesium etc. which are essential elements for the growth of seaweed as a mineral component is preferable.
In humic soil with insufficient fermentation, the content of fulvic acid is small and the effect is small. On the other hand, when it reaches a fully matured state, it becomes difficult to produce an oxygen-free state, and the effect may be reduced.

  In the present invention, iron hydroxide and / or iron oxide is generated by the reaction between the carbon material and the iron material, and it is desirable that the generated iron hydroxide and / or iron oxide is removed. This is because the presence of iron hydroxide and / or iron oxide in the vicinity of the interface between the two obstructs the contact between the two and inhibits the reaction. Therefore, in the present invention, an oxygen-free state is created by using humus, and iron hydroxide and / or iron oxide is efficiently removed.

Moreover, since the iron material used for this invention melts | dissolves from the location which contacted the carbon material, since it is necessary to replace | exchange the consumed iron material, it is continuous as shown in FIGS. It is preferable to adopt the structure of a general iron supply material.
Here, FIG. 2 is the figure which showed one example of the structure of the continuous iron supply material according to this invention. A natural fiber bag (for example, made of concrete or metal) is filled with humus, carbon, and iron with an oxygen content of 1% by mass or less in one natural fiber bag (one unit). Is charged.
FIG. 3 is a diagram showing an example of the natural fiber bag shown in FIG. 2, that is, one unit configuration. It is packed with humus, carbon, and iron.
Furthermore, FIG. 4 is the figure which showed one example of the structure of a carbon material and an iron material among the continuous iron supply materials according to this invention.

  In this invention, in order to elute iron effectively, as shown in FIG. 1, it is preferable that the iron material and the carbon material are used as the center of the iron supply material, and the humus soil is arranged on the outer periphery thereof.

Moreover, it can also wrap with the securing material which has a self-shrink property from the outer side of the said humus. This is because, with this configuration, the iron material and the carbon material can always come into contact stably. The lashing material in the present invention is preferably a mesh-shaped rubber material or a nylon net, but for example, it is simply fastened with a rubber string or tyed with a nylon thread or the like. To include.
The shape of the iron material and carbon material at that time is not particularly limited, but the iron material is particularly preferably rod-shaped. This is because it can be secured stably.
It is also possible to fill the cylindrical bamboo charcoal with an iron wire, or to fill a recess in the half-moon shaped bamboo charcoal with a wire.

The arrangement of the iron supply material in the present invention will be described with reference to FIG.
Fill the net or water-permeable container (or bag) with a combination of iron and carbon in humus. It is placed in a concrete box (shown as A in FIG. 5).
Alternatively, a bag containing only humus and a bag containing carbon material and iron material filled in another large bag is placed in a concrete box (shown as B or C in FIG. 5). )
Alternatively, an iron tube may be used instead of a concrete box. In this iron, a combination of iron and carbon materials in humus is filled into a net or a water-permeable container (or bag). Also, a bag containing only humus and a bag containing carbon material and iron material, both of which are filled in another large bag, is placed in an iron cylinder. In this case, the steel tube will dissolve after long-term use.

  The iron supply material according to the present invention can be effectively dissolved in the environmental water as an iron complex by installing it in a place (environmental water) where iron supply is required, that is, in a river, a lake, or the sea. Can be made.

[Example 1]
As the humus, SB (manufactured by Akagi Horticulture, hardwood) shown in FIG. 6 was used. The iron material is the iron wire shown in Fig. 7 (length: 50cm, diameter: 0.8mm, mass: 2.27g, annealed iron wire, JIS standard number: JIS G 3532, symbol: SMW-A), and granular iron material (Commonly called billet). As the carbon material, a carbon fiber fabric (20 cm × 15 cm, mass: 30 g) was used. Here, as a result of observing oxygen in the iron wire with an electron probe microanalyzer (electron beam microanalyzer), the presence of oxygen above the detection limit was not recognized. In addition, when both terminals of a simple tester were applied to charcoal, it was confirmed that current flowed.
The bundled iron wire was inserted into the mulch. When using an iron material and a carbon material, a bundle of iron wires was used in the carbon fiber fabric.

The container containing humus, iron, and carbon was a wide-mouth bottle (capacity: 2 L, made of polyethylene), and 1500 mL of water was added so that the humus, iron, and carbon were buried in water. Then, it was left standing with the lid of the wide-mouth bottle. As shown in Table 1, five types of sample aqueous solutions were prepared by changing the configuration of iron and carbon material.
Ten days later, each aqueous solution was drawn out and preparations were made to measure the iron concentration by the ICP method (inductively coupled plasma emission spectrometry). The aqueous solution pumped out of the container was freed from solids with a draining net. Ion exchange water: about 25 mL was placed in a 50 mL volumetric flask, and an aqueous sample solution: 5 mL and 12 M HCl: 0.5 mL were added thereto. Next, ion-exchanged water was added to dilute accurately to 50 mL. The diluted sample aqueous solution was filtered through a minisalt having a pore size of 0.45 μm. The iron concentration was measured by the ICP method.
The measurement results are also shown in Table 1.

From the table, it can be seen that the iron concentration was increased 13.6 times by coexisting with the iron material (1-2) than in the case of humus alone (1-1). Furthermore, it is understood that the iron concentration is 18.0 times higher than that of humus alone by contacting with the carbon material (1-3).
After measuring the iron concentration, the aqueous solution in the container was taken out and fresh water was added. Ten days later, the same treatment was performed, and the iron concentration was measured. It turns out that iron concentration became 12.2 times larger by making it coexist with an iron material (1-2) rather than the case (1-1) of humus alone. Furthermore, it is found that the iron concentration became 20.9 times higher by contacting with the carbon material (1-3).

On the other hand, when granular iron was used as the iron material, the concentrations were 8.7 times (1-4) and 10.5 times (1-5). From these experimental results, when the carbon material and the iron material were brought into contact with the humus, the amount of dissolved iron was remarkably improved.
Further, 10 days after the water was changed (20 days after the start of the experiment), the aqueous solution in the container was taken out and subjected to the same treatment as above, and the iron concentration was measured. The iron concentration became 9.1 times larger by coexisting with the iron material (1-4) than in the case of humus alone (1-1). Furthermore, iron concentration became 10.8 times as high concentration by making it contact with a carbon material (1-5).

[Example 2]
We investigated whether the dissolution of iron in humus was the same in seawater.
The humus used 160g of SB. As the iron material, the annealed iron wire of Example 1: 150 g or the granular iron material (billet): 150 g was used. As the carbon material, a carbon fiber fabric (20 cm × 15 cm, mass: 30 g) was used. The iron material was inserted into the humus. When using an iron material and a carbon material in combination, they were used by being wrapped in a carbon fiber fabric. A wide-mouth bottle (capacity: 2 L, made of polyethylene) was used as a container for containing these. A 3% -sodium chloride aqueous solution having a salt concentration similar to seawater was used, and 1500 mL of this was added so that the humus, iron, and carbon materials were immersed in water, and then the container was held in a covered state. Five types of sample aqueous solutions shown in Table 2 were prepared by changing the configuration of iron and carbon material.

The experiment started on February 20, 2013. After 7 days, the aqueous solution was drawn out and preparations for measuring the iron concentration were made. The aqueous solution pumped out of the container was freed from solids with a draining net. Aqueous sample: 5 mL and 12 M HCl: 0.5 mL were added to a volumetric flask containing about 25 mL of ion-exchanged water. Next, ion-exchanged water was added to dilute accurately to 50 mL. The diluted sample aqueous solution was filtered through a minisalt having a pore size of 0.45 μm. The iron concentration was measured by the ICP method.
The measurement results are also shown in Table 2.

From the table, in the case of humus alone, the iron concentration in (2-1) was 0.36 mg / L, but when iron material was added (2-2), it was 42.6 mg / L, 118 times higher. Furthermore, when the carbon material was brought into contact with the iron material (2-3), it was 76.4 mg / L, which was 212 times higher than that of the humus alone. Iron dissolution was accelerated 1.8 times depending on the presence or absence of carbon material.
On the other hand, when granular iron was used as the iron material, it was about 4.9 times (2-4) of humus alone, and about 7.0 times when combined with carbon material (2-5). As the iron material to be used, a linear iron material was more effective than granular iron.

Example 3
Using 3% -sodium chloride and humus / iron wire, humus / iron wire / carbon fiber fabric, the elution amount of iron when the salt solution was changed every day was determined.
The humus was 100 g of SB, and the iron material was 100 g of the annealed iron wire of Example 1. As the carbon material, a carbon fiber fabric (35 cm × 15 cm, mass: 50 g) was used.
When using an iron material alone, the iron material was inserted into humus. When using an iron material and a carbon material in combination, they were used by being wrapped in a carbon fiber fabric.
As a container for these, a wide-mouth bottle (capacity: 1 L, made of polyethylene) was used. Sample 3-1 contained humus and iron, and sample 3-2 contained humus, iron and carbon material (carbon fiber). In this container, 700 mL of a 3% -sodium chloride aqueous solution having a salt concentration similar to seawater was added so that the humus, iron, and carbon materials were immersed in water, and then the container was held in a covered state. .

The experiment started on March 21, 2013. One day later, the container was tilted to almost draw out the aqueous solution, and 700 ml of a newly prepared 3% -sodium chloride aqueous solution was added.
After a predetermined period of time, a sodium chloride aqueous solution in the container was drawn out and a new sodium chloride aqueous solution was added. The exchange dates were 1 day, 4 days, 5 days, 6 days, 7 days, 8 days, and 11 days later.
The prepared liquid in the container was prepared for measuring the iron concentration. The aqueous solution pumped out of the container was freed from solids with a draining net. Aqueous sample: 5 mL and 12 M HCl: 0.5 mL were added to a volumetric flask containing about 25 mL of ion-exchanged water. Next, ion-exchanged water was added to dilute accurately to 50 mL. The diluted sample aqueous solution was filtered through a minisalt having a pore size of 0.45 μm. The iron concentration was measured by the ICP method.
The measurement results are also shown in Table 3.

From Table 3, the iron concentration in the case of humus / iron after 1 day was (1) 10.6 mg / L, but when carbon material was added, it became 32.1 mg / L, which was about three times as high. .
In either case, the amount of iron elution was increased by adding a carbon material. By accumulating the measured values for each of the seven measurements, the melting of iron was promoted 1.5 times by adding the carbon material.

  Other embodiments not described above, for example, carbon fiber reinforced plastic, expanded graphite sheet, charcoal, graphite material, carbon material, and bamboo charcoal are the same as in the above examples, It has been confirmed that it has an excellent iron elution effect.

  In the present invention, it is important that at least a part of the carbon material and the iron material are in contact with each other, and it is needless to say that the shape and the contact mode can be appropriately changed according to the actual installation conditions of the iron supply material.

By utilizing the iron supply material according to the present invention, chlorophyll can be increased, seaweeds and seaweeds can be propagated, water quality can be purified, sludge can be decomposed, and the transparency of the sea can be improved.
It also prevents sea burning and breeds seafood.
Furthermore, global warming can be prevented through the absorption of carbon dioxide by seaweed and the effect of promoting dissolution of atmospheric carbon dioxide into seawater.

Claims (6)

An iron supply material for supplying iron to environmental water, comprising humus, a carbon material, and an iron material having an oxygen content of 1% by mass or less, and at least a part of the carbon material and the iron material are in contact with each other And the iron supply material which makes the said iron material and the said carbon material the center of the said iron content supply material, and has arrange | positioned the said humus soil on the outer periphery .   The iron supply material according to claim 1, wherein the iron material is pure iron having an oxygen content of 1% by mass or less. The iron supply material according to claim 1 or 2, wherein the electric conductivity of the carbon material is 10 ³ Ω · cm or less in volume resistivity.   The iron supply material according to any one of claims 1 to 3, wherein the carbon material is at least one selected from carbon fiber reinforced plastic, expanded graphite sheet, charcoal, graphite material, carbon material, bamboo charcoal, and carbon fiber. . The iron supply material according to any one of claims 1 to 4 , wherein the iron supply material is wrapped with a self-shrinking binding material from the outside of the mulch. The iron component according to any one of claims 1 to 5 , wherein the iron component is installed in at least one environmental water selected from among rivers, lakes and seas, and iron is eluted into the environmental water as an iron complex. Supply method.